Method and apparatus for the continuous production of carbon disulphide



1954 E. CHARLES 2,670,277

METHOD AND APPARATUS FOR THE CONTINUOUS PRODUCTION OF CARBON DISULPHIDEFiled June 10, 1949 fiver/far:

Ere/ven- CHARLES Patented Feb. 23, 1954 METHOD. AND APPARATUS FOR THECON- TINUOUS PRODUCTION OF CARBON DI- SULPHIDEK Ernest Charles, Clamecy,France, assignorto Soci'ete des Produits Chimiques de Clamecy Clamecy,France, a corporation of France- Application June .10, 1949,, Serial-No.98,346 Glaimspriority, application France June 12, 1948- 2Glaimsi IThis; invention relates to a method and to meansforreacting coalandsuliur-for the formation of carbon disulfi'de.

anobject" ortheinvention to-organize the formation of the carbondisul'fideinsuch manner as. to reduce to a minimum the amount of heatenergy to betintroduced-from the outside into the zone of reaction.

' Thenew methodis characterizedessentially by the introduction into thereaction zone, of thecoalfreed-from volatile gases and the sulfur afterbothhave been preheated to the reaction temperature. The losses of heatin this zone are prevented by heat insulating or slightly heating the,reaction vessel; the-heat produced in the reaction being utilizedunderthe-best possible conditionsfor preheating thesulphur and the coaland obtaining-theinexpensive purification of the carbondisulphide. f

It is known that the reaction between" sulfur and coal (which isendothermic at-"ordinary temperature) is exothermic at the reactiontemperature, ranging fromabout 900 and 1,000 C. Thus the productionofcarbon disulphide the heat energy tobe provided from the outside isconsumed in the preheating of the sulfur and the coal.

VWhenoperating batchwise with heat energy supplied from, the outsideunsatisfactory results, are obtained because" the: transmission ofheatthrough the charcoal layer'ispoor. Electric heat energyfori raisingthe-temperature, of the sulphur andthe coalis expensive. The mainobjection tow the introduction oflcharcoal at a low temperature into-theoven is that this product has a high gas content, so that. a large.amountof sulphur will be lost i'rrthe non-condensable gases.

Therefore according to the presentinvention the gases are removed from;the charcoal when heating; itand then exhausted from the; reaction oven.

'Eheequipment whereby the: new process may be carriedtinto efiectcomprises-essentiallyz-r averticalreaction retort having: little or noloss of heat, a vertical coal preheating retort, placed on top of the,reaction retort and. heated by means otiniected-air and gas, asuperheater adapted; to heat the sulphur vapor to the reactiontemperameans for melting; and. vaporizing the sulphur treated and forrectifying the carbon disulphide.

In. the drawing affixed to this specification and forming part thereofthe invention is illustrated diagrammatically by way of example.

Referring to the drawing coal (in any form, natural or agglomerated,with or without sulphuration catalysts or substances adapted to changethe melting temperature of the ashes) is fed into the hopper i. It isthen dischargedinto the heat-insulated coal preheating retort l0 throughthe medium of a gas-tight distributor 2. During itsdownwardtravel thecoal is heated by passing in front ofthe blast-pipe 9 fed with air'under pressure from a suitable source (not shown) through a conduit 8and with gases fed from the distillation of the charcoal through aconduit 1. The red-hot charcoal descends into the upper portionofthe'retort [3 which is kept under constant pressure by means of theautomatic reguIatorSB having its pressure-intake at $4. The coaldistillation gases aretaken up at 3 by the fan 4 and forced through theblast-pipe 9 into a hearth of the sulfur superheater" It. In order toprevent the vapor from penetratingi'ntothe coal pre-heatingretort Illa'very low pressure is maintainedin the bottom portion of this retort,and this very low pressure is transmitted-through the pressure intake Il to the automatic regulator 5. Due to the considerable loss of charge0c curring between the two ends of the pre-heating oven I0 the amount ofinert gas penetrating into the reaction retort I3 is insignificant. V

The solid sulphur introduced into the hopper 26 is fed by the screwconveyor 21 into the melting tunnel 24% provided wi'tl'r an agitator 23;This tunnel is heated by means of a cluster of tubularelements.

The molten sulphur passes through the filter 28 anoiis then fed tothebottom portion of thevaporizer 2i. The sulphur vapor is thensuperheated in the superheater l9 positioned in the compartment 2!? oithe'apparatus and is introduced at I 2 into the top-portionof thereactionv retortl3 Thefore-hearthl 8-is partially fed at- I 5 withthegases from the distillation of the coal in the pre-heating retort l0,the complementary heat units beingfed' through a conduit 6 from anysuitable source on the outside-. In addition airis' injected: at Hi,

The. combustion. gases during. their travel meet thesulphur: zit-Miamimelt it: and the molten sul:-.

phi-1r: is vaporized in; heater 2i. It is therefore apparent that thehot-gases and the-sulphur vapor. travel in a counter-current. The burntgases and sulphur; also. travel.v in; counter-current The burnt gasesescaping through the flue 25 and a stack (not shown).

The superheated sulfur vapor and the preheated coal react inside thereaction retort I3. The vapor of crude carbon disulphide (containingsulphur and non-condensable gases) passes through the shutters M to aheat exchange coil 31 in a column 36 where the crude carbon disulfideand intermixed gases are reduced in temperature after which such gasespass to the sulphur separating column 49. Liquid sulphur is sprinkledinto the top portion of the column 40 from a source presently to beexplained in order to bring about a separation of the sulphur containedin the crude disulfide gas fed into column 49 from coil 31. The carbondisulfide leaving the top of column 49 is free of sulphur and passesfrom such column into the top of a condenser 30. The carbon disulfide iscaused to condense in the condenser 30 and is drawn therefrom into acylinder 35 which receives both liquid carbon disulfide andnon-condensible gases. This carbon disulfide is free of sulphur but issaturated with dissolved sulphurated gases which are removed in thecolumn 36 by evaporization of such gases by means of the heattransferred to the column by coil 31, The pure carbon disulfide flowingfrom the lower section of column 36 is then cooled in a cooler 39. Thenon-condensible gases issuing from the cylinder 35 pass through a refluxcooler 31 and are then forced toward the plant exit by means of anextractor 32.

In order to supply the separating column 40 with the necessary liquidsulphur to effect the separation a part of the condensed carbondisulfide emanating from the column 39 and cylinder 35 is transferred bymeans of conduit 29 to the column 40 through a regulator valve 29 whichis controlled by the temperature at a selected point 40' in theseparating column 40. The substantially pure sulphur obtained at thebottom of separating column 46 is returned to the heater 2! by means ofa conduit 46.

The vapors removed from the carbon disulfide in column 36 are introducedby means of a conduit 45 into the upper end of column 30 along with thevapors received from column 49.

The coal ashes are extracted by means of a gas-tight cleaning device 42provided at the bottom of the reaction retort i3.

For starting the plant the reaction retort I3 is filled with coal whichis then ignited at some suitable points. Through the difierent nozzles14 air is blown in order to heat the coal to reaction temperature.

The reaction retort or oven 13 may be simply insulated with a convenientheat-insulating material. In this case the losses of heat should be lowso that the temperature of the mass is held at a level sufficient toobtain a satisfactory reaction between the sulphur with the coal.

Any losses of heat may be compensated by providing an external source ofheat.

On the other hand, the reaction retort [3 may be placed inside thesuperheating section H! where the pre-treatment of the sulphur componentis effected.

The sulphur vapor might also be directed to the bottom from the topportion thereof.

Various changes may be made in the process as well as in the means asdescribed by way of example in the above specification without departingfrom the spirit of the invention or sacrificing the advantages thereof.

I claim:

1. Apparatus for producing carbon disulflde,

comprising in combination, a vertically extending heat-insulatedreaction retort, a vertically extending heat-insulated preheatingchamber positioned above said retort and having its lower portion incommunication with thejupperportion of said retort, means for feedingcarbonaceous material into the upper portion of said preheating chamber,a burner for injecting a combustible gas and air into an intermediateportion of said chamber for combustion therein for heating saidcarbonaceous material whereby heated carbonaceous material is deliveredinto said retort, a gas pump for withdrawing combustible gas from theupper portion of said preheating chamber and a conduit for returning aportion thereof to said burner, a sulfur vaporizing and superheatingfurnace, a conduit for supplying another portion of said combustible gasto said furnace, a burner for burning said other portion of saidcombustible gas in said furnace to produce heat for vaporizing sulfurand superheating the resulting vapor, a conduit for supplying theresulting superheated sulfur vapor to the upper portion of said retort,and a conduit for withdrawing crude carbon disulfide vapors from thelower portion of said retort.

2. Apparatus for producing carbon disulfide, comprising in combination,a vertically extending heat-insulated reaction retort, a verticallyextending heat-insulated preheating chamber positioned above said retortand having its lower portion inconstantly open communication with theupper portion of said retort, feeding means for feeding carbonaceousmaterial into the upper portion of said preheating chamber, said feedingmeans including a sealing device for restricting entrance of air intosaid preheating chamber through said feeding means, a burner positionedintermediate the upper and lower portions of said preheating chamber forintroducing a mixture of air and combustible gas into said preheatingchamber for combustion therein, whereby heated carbonaceous material isdelivered into said retort, a gas pump for withdrawing gases due to saidcombustion from the upper portion of said preheating chamber to prevententrance of said gases into said retort, sulfur vaporizing apparatusincluding a burner, a conduit for delivering a portion of the gases fromsaid gas pump to said burner, a conduit for delivering sulfur gases fromsaid vaporizing apparatus into the upper portion of said retort, and aconduit for withdrawing crude carbon disulfide vapors from the lowerportion of said retort.

ERNEST CHARLES.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 1,615,659 Siedler Jan. 25, 1927 1,918,033 Griswold July 11,1933 2,046,818 Harkness July 7, 1936 2,052,297 Iddings Aug. 25, 19362,079,017 Iddings et a1 May 4, 1937 2,107,264 Baxter Feb. 1, 19382,141,758 Merriam Dec. 27, 1938 2,392,629 Avery Jan. 8, 1946 2,443,854Ferguson June 22, 1948 2,480,639 Ferguson Aug. 30, 1949

1. APPARATUS FOR PRODUCING CARBON DISULFIDE, COMPRISING IN COMBINATION,A VERTICALLY EXTENDING HEAT-INSULATED REACTION RETORT, A VERTICALLYEXTENDING HEAT-INSULATED PREHEATING CHAMBER POSITIONED ABOVE SAID RETORTAND HAVING ITS LOWER PORTION IN COMMUNICATION WITH THE UPPER PORTION OFSAID RETORT, MEANS FOR FEEDING CARBONACEOUS MATERIAL INTO THE UPPERPORTION OF SAID PREHEATING CHAMBER, A BURNER FOR INJECTING A COMBUSTIBLEGAS AND AIR INTO AN INTERMEDIATE PORTION OF SAID CHAMBER FOR COMBUSTIONTHEREIN FOR HEATING SAID CARBONACEOUS MATERIAL WHEREBY HEATEDCARBONACEOUS MATERIAL IS DELIVERED INTO SAID RETORT, A GAS PUMP FORWITHDRAWING COMBUSTIBLE GAS FROM THE